AU2014230978A1

AU2014230978A1 - Two-component adhesive for bonding artificial teeth to a denture base

Info

Publication number: AU2014230978A1
Application number: AU2014230978A
Authority: AU
Inventors: Stefan Aechtner
Original assignee: Vita Zahnfabrik H Rauter GmbH and Co KG
Current assignee: Vita Zahnfabrik H Rauter GmbH and Co KG
Priority date: 2013-03-11
Filing date: 2014-03-10
Publication date: 2015-08-13
Anticipated expiration: 2034-03-10
Also published as: ES2750476T3; WO2014139932A1; AU2014230978B2; US9918908B2; EP2970632B1; CN105008448A; CA2899710A1; EP2970632A1; CN105008448B; CA2899710C; DK2970632T3; US20160015604A1

Abstract

A mixture containing at least one first component A and at least one second component B, characterized in that said at least one first component A comprises a methyl methacrylate, a copolymer of methyl methacrylate dissolved in excess methyl methacrylate, optionally comprising, additionally dissolved therein, atleast one polyfunctional (meth)acrylate, especially ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, diurethane dimeth- acrylate, bis(hydroxymethacryloyloxypropoxy)phenylpropane (bis-GMA), polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylol- propane tetraacrylate;and a peroxide-based free-radical initiator, wherein said copolymer of methyl methacrylate is present in an amount of 30-50 parts by weight dissolved in a solution of 65-85 parts by weight of monomeric methyl methacrylate and 3-15 parts by weight of the polyfunctional (meth)acrylate, especially the triethylene glycol dimethacrylate (TEGDMA), mixed with a solution of 0.5 to 3 parts by weight of said peroxide-based free-radical initiator, especially dibenzoyl peroxide, in 70-90 parts by weight of monomeric methyl methacrylate, and said at least one second component B comprises methyl methacrylate and a tertiary amine.

Description

WO 2014/139932 PCT/EP2014/054553 Two-Component Adhesive For Bonding Artificial Teeth to a Denture Base The present invention relates to a mixture containing at least one first component A and at least one second component B, to a dental prosthesis with a denture base and artificial teeth erected therein, and to uses of the mixture according to the 5 invention. Bonds between finished denture bases and teeth have previously been prepared by pretreating the adherend surfaces with primers. The primer partially dissolves the surface of the components to be bonded and enables improved penetration of the adhesive into the topmost substrate layers and thus achieves a higher strength of 10 the adhesive bond. The pretreatment with primers is disadvantageous because it requires an additional operation. Such an additional operation is counterproductive, in particular, in modern mechanical production processes for partial or full prosthe ses. Therefore, it is desirable to provide an adhesive that can permanently bond artificial teeth to the denture base without pretreatment with primers. 15 US 4,182,035 A discloses a composition for bonding hard tissues of the human body. It essentially contains a free-radically polymerizable polymer and a curing system containing a peroxide, an amine or salt thereof, and a salt of sulfinic acid. EP 0 452 540 Al discloses an adhesive for bonding molded parts of polycarbonate plastics. 20 A cold-curing two-component polymerization adhesive based on solutions of poly(methyl methacrylate) in alkyl methacrylate that additionally contain a di and/or trimethacrylate can be used, in a temperature range of from -35 *C to +85 *C, to prepare strong adhesive bonds between molded parts of polycarbonate that are resistant to water and fuels. 25 US 6,734,249 B1 describes an acrylate adhesive that cures at room temperature and has an excellent dimensional stability. Such adhesives can be used, in particular, in applications for optical fiber connectors. Mixtures consisting of two parts are disclosed, wherein the first part contains one or more monofunctional, WO 2014/139932 PCT/EP2014/054553 -2 difunctional or trifunctional acrylates or acrylate monomers, a peroxide or hydroperoxide as initiator, and antioxidants and other additives. The second part represents an activator, which may contain, for example, N,N-disubstituted aromatic amines, a difunctional methacrylate monomer, an antioxidant, and 5 optionally additives, such as thickeners, thixotropic agents and the like. JP 55110174 or CN 200810198970 describe adhesive mixtures. US 2004/0002037 Al describes a method of securing a dental post in a corre spondingly prepared tooth, crown or bridge. For securing, there is used a self curing two-component cement prepared on the basis of an acrylate resin, and 10 whose components are not mixed before application. The cement may also contain an aromatic tertiary amine and other components, such as an organic peroxide. Other additives may optionally be present. US 4,792,577 discloses an orthodontic adhesive consisting of two components that become reactive and cure without mixing when two layers of the different compo 15 nents come into contact. The first component has a relatively low viscosity and contains an acrylic or methacrylic diester of ethoxylated bisphenol A, an acrylic or methacrylic diester of an alkanediol, and benzyl acrylate or methacrylate. The second component contains a filler and an acrylic or methacrylic diester of ethoxylated bisphenol A, an acrylic or methacrylic diester of an alkanediol, and 20 benzyl methacrylate or acrylate, wherein said filler is present in amounts within a range of from 50 to 80% by weight, based on the second component. One of the mentioned components contains a peroxide-based catalyst, and the other compo nent contains a tertiary amine as activator for the peroxide catalyst. It is the object of the present invention to provide a mixture that can permanently 25 bond artificial teeth to a denture base that, like the artificial teeth, is made of poly (meth)acrylate or its copolymers, leading to a prosthesis that will not result in adhesive failure of the bond upon critical load. The object of the invention is achieved by a mixture containing at least one first component A and at least one second component B, characterized in that WO 2014/139932 PCT/EP2014/054553 -3 said at least one first component A comprises a methyl methacrylate, a copolymer of methyl methacrylate dissolved in excess methyl methacrylate, optionally comprising, additionally dissolved therein, at least one polyfunctional (meth)acrylate, especially ethylene glycol dimethacrylate, butanediol 5 dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, diurethane dimethacrylate, bis(hydroxymethacryloyloxypropoxy)-phenylpropane (bis-GMA), polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate; and a peroxide-based free-radical initiator, wherein said copolymer 10 of methyl methacrylate is present in an amount of 30-50 parts by weight dissolved in a solution of 65-85 parts by weight of monomeric methyl methacrylate and 3-15 parts by weight of the polyfunctional (meth)acrylate, especially the triethylene glycol dimethacrylate (TEGDMA), mixed with a solution of 0.5 to 3 parts by weight of said peroxide-based free-radical initiator, especially dibenzoyl peroxide, in 70-90 15 parts by weight of monomeric methyl methacrylate, and said at least one second component B comprises methyl methacrylate and a tertiary amine. Figure 1 shows a test specimen with a prosthetic tooth. Figure 2 shows a section along the line II---II of Figure 1. Figure 3 shows a test specimen after a fracture test with a prosthetic tooth bonded 20 with the adhesive according to the invention. Figure 4 shows a double section along the lines IV---IV and IV'---IV' through the test specimen of Figure 3, taking into account the situation where even parts of the test specimen may be torn off during excavation. Figure 5 shows a test specimen after a fracture test with a prosthetic tooth bonded 25 with a conventional adhesive. Figure 6 shows a double section along the lines VI---VI and VI'---VI' through the test specimen of Figure 5.

WO 2014/139932 PCT/EP2014/054553 -4 In another embodiment of the invention, said at least one first component A of the mixture according to the invention may comprise one or more polyfunctional (meth)acrylates, for example, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate 5 (TEGDMA), tetraethylene glycol dimethacrylate, diurethane dimethacrylate, bis(hydroxymethacryloyloxypropoxy)phenylpropane (bis-GMA), polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylolpropane tetraacrylate, etc. According to the invention, the copolymer of methyl methacrylate is dissolved in 10 an excess of methyl methacrylate in said at least one component A of the mixture according to the invention. In another embodiment of the invention, at least one of the mentioned polyfunctional (meth)acrylates, for example, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, diurethane 15 dimethacrylate, bis(hydroxymethacryloyloxypropoxy)phenylpropane (bis-GMA), polyethylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditri methylolpropane tetraacrylate, etc., may be present dissolved in component A. In another embodiment of the present invention, said at least one component A may be obtainable by dissolving the copolymer of methyl methacrylate in mono 20 meric methyl methacrylate in the presence of at least one of the mentioned polyfunctional (meth)acrylates, for example, ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimeth acrylate (TEGDMA), tetraethylene glycol dimethacrylate, diurethane dimeth acrylate, bis(hydroxymethacryloyloxypropoxy)phenylpropane (bis-GMA), polyeth 25 ylene glycol dimethacrylate, trimethylolpropane trimethacrylate, ditrimethylol propane tetraacrylate, etc., and mixing with a solution of dibenzoyl peroxide in monomeric methyl methacrylate. Typically, said tertiary amine present in the mixture according to the invention in said at least one component B is N,N-dimethyl-p-toluidine. In particular, said 30 tertiary amine may be dissolved in amounts of 1-5 parts by weight in the form of WO 2014/139932 PCT/EP2014/054553 -5 N,N-dimethyl-p-toluidine in 65-85 parts by weight of monomeric methyl methacry late. The present invention also relates to a dental prosthesis with a denture base and artificial teeth erected therein, characterized in that said artificial teeth are 5 permanently bonded to the denture base by means of the mixture according to the invention. The present invention also relates to the use of the mixture according to the invention as a two-component adhesive, especially for preparing the dental prosthesis according to the invention. Typically, according to the invention, the 10 mixture according to the invention may be used for bonding artificial teeth, especially made of PMMA and/or its copolymers, to a denture base, especially made of PMMA and/or its copolymers. The present invention also relates to the use of the mixture according to the invention as a clear coat for sealing dental restorations, or of mixtures according to 15 the invention colored by means of corresponding pigments for painting dental restorations. The present invention also relates to a process for preparing the dental prosthesis according to the invention, characterized in that the artificial teeth are permanently bonded to the denture base by applying the mixture according to the invention to 20 the areas of the artificial teeth coming into contact with the denture base, and/or applying the mixture according to the invention to the surfaces of the areas in the denture base in which the artificial teeth are arranged, and by curing the mixture. The prostheses obtained with the mixture according to the invention were subject ed to fracture tests according to the standard DIN 13998. Experience has shown 25 that adhesive failure of the adhesive is to be expected without previous pretreat ment of the adherend sites with a primer. This was also confirmed experimentally for prosthetic teeth bonded with conventional adhesives (Figures 5 and 6). Surprisingly, the prostheses prepared with the mixture according to the invention WO 2014/139932 PCT/EP2014/054553 -6 exclusively showed cohesive fracture surfaces in the teeth and/or denture base (Figure 3, 4). The invention is further described hereinafter by means of the Examples. Example 1: 5 50 g of the copolymer of methyl methacrylate (Degacryl* MW 332, Evonik, Germany) is dissolved in a mixture of 100 g of methyl methacrylate and 10 g of triethylene glycol dimethacrylate (TEGDMA) supplied by Lehmann & Voss & Co., Germany (Luvomaxx® TEDMA). Thereafter, 2 g of dibenzoyl peroxide is dissolved in 80 g of methyl methacrylate, and to this solution is added 120 g of the first 10 solution to obtain component A. Component B is prepared as follows: 3 g of N,N-dimethyl-p-toluidine is dissolved in 75 g of methyl methacrylate. Example 2: Component A as prepared in Example 1 was mixed with the mentioned component 15 B at a ratio of 2:1 at room temperature. The mixture was applied either to the areas of the denture base coming into contact with the basal surface of the teeth, and/or to the basal surface of the artificial teeth, for example, with a paintbrush. The thus prepared prosthetic teeth were placed into the respective alveoli of the base. The thus prepared prosthesis was stored over night in an annealing furnace 20 at 37 *C for the adhesive to cure. With test specimens prepared in the same way (Figures 1 and 2), fracture tests according to the standard DIN 13998 were performed. The prostheses exclusively showed cohesive fracture areas in the teeth and/or base (Figures 3 and 4). List of reference symbols: 25 1. Test specimens for fracture tests according to DIN 13998 WO 2014/139932 PCT/EP2014/054553 -7 2. Prosthetic tooth bonded into the test specimen 3. Remnant of the prosthetic tooth after cohesive failure 4. Adhesive residues

Claims

1. A mixture containing at least one first component A and at least one second component B, characterized in that said at least one first component A comprises a methyl methacrylate, a 5 copolymer of methyl methacrylate dissolved in excess methyl methacrylate, optionally comprising, additionally dissolved therein, at least one polyfunctional (meth)acrylate, especially ethylene glycol dimethacrylate, butanediol dimethacrylate, hexanediol dimethacrylate, triethylene glycol dimethacrylate (TEGDMA), tetraethylene glycol dimethacrylate, diurethane 10 dimethacrylate, bis(hydroxymethacryloyloxypropoxy)phenylpropane (bis GMA), polyethylene glycol dimethacrylate, trimethylolpropane trimeth acrylate, ditrimethylolpropane tetraacrylate; and a peroxide-based free radical initiator, wherein said copolymer of methyl methacrylate is present in an amount of 30-50 parts by weight dissolved in a solution of 65-85 parts 15 by weight of monomeric methyl methacrylate and 3-15 parts by weight of the polyfunctional (meth)acrylate, especially the triethylene glycol dimethacrylate (TEGDMA), mixed with a solution of 0.5 to 3 parts by weight of said peroxide-based free-radical initiator, especially dibenzoyl peroxide, in

70-90 parts by weight of monomeric methyl methacrylate, and said at least 20 one second component B comprises methyl methacrylate and a tertiary amine. 2. The mixture according to claim 1, characterized in that said at least one component A is obtainable by dissolving the copolymer of methyl methacry late in monomeric methyl methacrylate in the presence of at least one 25 polyfunctional (meth)acrylate, especially triethylene glycol dimethacrylate (TEGDMA), and mixing with a solution of dibenzoyl peroxide in monomeric methyl methacrylate. 3. The mixture according to claim 1 or 2, characterized in that said tertiary amine in said at least one component B is N,N-dimethyl-p-toluidine. WO 2014/139932 PCT/EP2014/054553 -9 4. The mixture according to claim 3, characterized in that 1-5 parts by weight of N,N-dimethyl-p-toluidine is dissolved in 65-85 parts by weight of mono meric methyl methacrylate. 5. The mixture according to at least one of claims 1 to 4, characterized in that 5 pigments for coloring are present in the mixture. 6. A dental prosthesis with a denture base and artificial teeth erected therein, characterized in that said artificial teeth are permanently bonded to the den ture base by means of the mixture according to at least one of claims 1 to 5. 10 7. Use of the mixture according to any of claims 1 to 6 as a two-component adhesive. 8. The use according to claim 7 for preparing a dental prosthesis according to claim 6. 9. Use of the mixture according to any of claims 1 to 5 for bonding artificial 15 teeth, especially made of PMMA and/or its copolymers, to a denture base, especially made of PMMA and/or its copolymers. 10. Use of the mixture according to at least one of claims 1 to 5 as a clear coat for sealing dental restorations. 11. Use of the mixture according to at least one of claims 1 to 5 as a lacquer for 20 painting dental restorations. 12. A process for preparing a dental prosthesis according to claim 6, character ized in that the artificial teeth with the denture base are prepared by apply ing the mixture according to at least one of claims 1 to 5 to the areas of the artificial teeth coming into contact with the denture base, and/or applying 25 the mixture according to at least one of claims 1 to 5 to the surfaces of the areas in the denture base in which the artificial teeth are arranged, and af- WO 2014/139932 PCT/EP2014/054553 - 10 ter inserting the artificial teeth into the denture base and after curing the mixture, a permanent bond of the artificial teeth with the denture base is formed.